Organic Electroluminescent Diode And Diode Panel With Anti-Reflective Coating Conducive To The Emission Of Light

ABSTRACT

The diode comprises an organic electroluminescent layer interposed between a lower electrode and a partially transparent and semireflective upper electrode, which itself comprises a transparent conducting sublayer and a current-distributing metal sublayer, for example an opaque grid. A dielectric antireflection layer is deposited on the grid to improve the emission contrast in ambient light, which grid, according to an advantageous embodiment, is designed to optimize the semireflective properties of the upper electrode, thereby improving, by an optical cavity effect, extraction of the emitted light.

The invention relates to an organic light-emitting diode capable of emitting light, comprising:

-   -   a substrate;     -   an organic electroluminescent layer interposed between a lower         electrode and a partially transparent upper electrode comprising         a transparent, conducting sublayer, which is continuous and of         uniform thickness, and an opaque current-distributing metal         sublayer that has windows for passage of the light emitted by         the electroluminescent layer; and     -   a transparent dielectric antireflection layer in contact, via         its external face, with a medium, generally air, and, via its         internal face, with said transparent conducting sublayer and         said opaque metal sublayer.

This is therefore what is called a “top-emitting” diode (i.e. one that emits on the opposite side from the substrate). Such diodes may have a conventional structure, in which case the upper electrode is a cathode, or reverse structure, in which case the upper electrode is an anode.

The upper electrode of this diode is therefore at least a bilayer comprising a transparent conducting main sublayer, ensuring uniform distribution of the electrical charges into the electroluminescent layer so as to create a uniform electric field in the thickness of this layer, and an opaque current-distributing sublayer, for example a metal grid that essentially serves to increase the conductivity of the upper electrode and between the bars of which the light emitted in the electroluminescent layer can pass.

The invention also relates to arrays of these diodes, especially those that form illumination or display, especially image display, panels.

Reflection of the ambient light of the opaque current-distributing sublayer, for example, on the bars of the abovementioned grid, greatly degrade the emission contrast of the diode in ambient light. By applying an antireflection layer of uniform thickness, that is to say as a “complete layer”, over the entire active surface of the diode, it is possible to solve this problem, but this antireflection layer then risks degrading the overall transparency of the upper electrode and consequently the luminous efficiency of the diode.

One object of the invention is to provide an optimum compromise between the antireflection function of such a layer in the opaque zones of the upper electrode and the overall transparency of the upper electrode so as to guarantee the best performance in terms of extracting the light emitted by the diode through this electrode.

For this purpose, one subject of the invention is an organic light-remitting diode capable of emitting light, comprising:

-   -   a substrate;     -   organic electroluminescent layer capable of emitting light,         interposed between a lower electrode and a partially transparent         upper electrode, which are designed to pass a current, through         the organic electroluminescent layer and thus cause, within this         layer, the emission of light,         said upper electrode comprising a transparent conducting         sublayer of approximately uniform thickness and a metal sublayer         for distributing the current, which is distributed in opaque         zones between which there are gaps in this sublayer that form         windows for passage of the light emitted by the         electroluminescent layer; and     -   a transparent dielectric antireflection layer of approximately         uniform thickness in contact, via its external face, with a         medium, generally air, and, via its internal face, with said         transparent conducting sublayer and said opaque metal sublayer,         characterized in that the material and the thickness of said         dielectric antireflection layer are chosen with the material of         said current-distributing metal sublayer so that the reflectance         of said opaque zones, measured at normal incidence at a         wavelength λ_(amb) close to 550 nm, is less than 0.1.

The lower electrode itself is therefore interposed between the substrate and the electroluminescent layer.

The transparent conducting sublayer of the upper electrode is generally based on a semiconductor oxide such as ITO (indium tin oxide). It is also possible to use a metal sublayer of very small thickness. It covers the entire active surface of the diode and normally does not have holes. Its thickness is generally constant over the entire active surface of the diode.

The current-distributing metal sublayer on the other hand has many holes or gaps for the passage of light. Its thickness is therefore not uniform over the entire active surface of the diode. Between these “windows”, the thickness of this metal sublayer is large enough to prevent the passage of light. The emitted light or the ambient light is generally reflected off these opaque zones.

The transparent dielectric antireflection layer is in contact, via its internal face, on the one hand, with the current-distributing metal sublayer at the places of the opaque zones and, on the other hand, with the transparent conducting sublayer through the windows in the metal sublayer.

The wavelength λ_(amb) corresponds to the approximate wavelength, of the maximum emittance in ambient light, taking into account the spectral sensitivity of the human eye.

The upper electrode is only partially transparent because, at the places of the opaque zones where the current-distributing metal sublayer covers the transparent conducting sublayer, the light emitted by the electroluminescent layer is absorbed or reflected by this electrode. These covering zones are therefore opaque zones.

In contrast, the light emitted by the electroluminescent layer passes through the upper electrode via the windows or holes made between the opaque zones of the current-distributing metal sublayer. The surface conductivity of this metal sublayer is, at the places of these opaque zones, preferably at least ten times greater than that of the subjacent transparent conducting sublayer so as to ensure that the current flowing in the electrode is effectively distributing.

According to the invention, the transparent dielectric layer therefore provides an optimum antireflection function for the reflective surface of the opaque current-distributing conducting sublayer with respect to ambient light. The emission contrast of the diode in ambient light is therefore improved.

Preferably, if n₁ is the optical index of said medium at the wavelength λ_(amb), the material of index n₂ (λ_(amb)) measured at the wavelength λ_(amb), and the thickness d₂ of said dielectric antireflection layer are chosen with the material of index ñ₃ of said current-distributing metal sublayer, which is measured at the same wavelength λ_(amb) and is defined by its argument n₃ and its phase Φ in such a way that ñ₃=n₃e^(iΦ), so as to approximately satisfy the equation:

${n_{2}\left( \lambda_{amb} \right)} = \frac{\sqrt{{- \left( {{n_{1}{\cos (\varphi)}} - n_{3} + {n_{3}{\sin^{2}(\varphi)}}} \right)}n_{3}{n_{1}\left( {{n_{1}{\sin^{2}(\varphi)}} + {n_{3}{\cos (\varphi)}} - n_{1}} \right)}}}{- \left( {{n_{1}{\sin^{2}(\varphi)}} + {n_{3}{\cos (\varphi)}} - n_{1}} \right)}$

Thanks to the choice of materials, especially of the antireflection layer and the current-distributing layer, a low or very low reflectivity of the ambient light on the opaque zones of the upper electrode is then, obtained, thereby appreciably improving the emission contrast of the diode in ambient light.

Furthermore, and to supplement the antireflection function, preferably the material, of index n₂ (λ_(amb)) measured at a wavelength λ_(amb) close to 550 nm, and the thickness d₂ of said dielectric antireflection layer are chosen so as to approximately satisfy the equation:

$d_{2} = {\frac{\lambda_{amb}}{4{n_{2}\left( \lambda_{amb} \right)}}\left( {p - \frac{\varphi_{2 - 3}}{\pi}} \right)}$

where p is any even integer and where  ₂₋₃ is the phase shift of a light ray of wavelength λ_(amb) after reflection at the interface between the dielectric antireflection layer and the current-distributing metal sublayer.

The equation giving the value of d₂ expresses here the destructive interference of the ambient light within the dielectric antireflection layer.

Thanks to this thickness of the antireflection layer, a low or very low reflectivity of the ambient light on the upper electrode is then obtained, thereby further improving the emission contrast of the diode in ambient light.

Preferably, the material of said dielectric antireflection layer and the material of said current-distributing metal sublayer are, respectively:

-   -   either silicon nitride and tantalum;     -   or titanium oxide and a metal from among nickel, chromium,         titanium and vanadium;     -   or zinc selenide and a metal from among nickel, chromium,         titanium and vanadium.

Preferably, the diode also includes a lower reflecting layer suitable for reflecting said emitted light, which layer is interposed between said substrate and said organic electroluminescent layer or is incorporated into the substrate.

Thanks to this lower reflecting layer, the extraction of the emitted light and the luminous efficiency of the diode are substantially improved.

Preferably, this lower reflecting layer is an integral part of the lower electrode and is therefore generally metallic or opaque.

According to other possible embodiments:

-   -   this lower reflecting layer is interposed between the substrate         and the lower electrode, which is therefore transparent or         semitransparent;     -   this lower reflecting layer is interposed between the lower         electrode and the organic electroluminescent layer; and     -   this lower reflecting layer is an integral part of the         substrate. In the case of a substrate formed from an active         matrix, the lower reflecting layer may be formed by one of the         layers of the active matrix.

This lower reflecting layer may be made of a dielectric and have a multilayer structure (Bragg reflector).

Preferably, the diode furthermore includes a semireflective upper layer suitable for partially reflecting said emitted light, which layer is interposed between said organic electroluminescent layer and the upper electrode and/or is incorporated into this upper electrode.

The semireflective upper layer may comprise the current-distributing metal layer, the opaque zones then serving as reflectors, reflecting toward the electroluminescent layer.

The upper electrode itself, or a sublayer of which it is composed, may form this semireflective upper layer. If the organic electroluminescent layer comprises highly doped organic sublayers, as illustrated in documents EP 0 498 979 or EP 1 017 118, the transparent conducting sublayer is preferably metallic and itself advantageously forms the semireflective upper layer. In the other cases, the upper electrode may also include a charge-injection sublayer interposed between the organic electroluminescent layer and the transparent conducting sublayer, serves as a semireflective upper layer.

In these other cases, if the upper electrode is a cathode, a metal with a low work function, such as calcium, is chosen for it; it is also possible to use a mixture of the LiF+Al type. If the upper electrode is an anode, a metal with a high work function, such as silver or gold, is chosen for it.

The upper electrode may include a diffusion barrier sublayer which is interposed between the organic electroluminescent layer and the transparent conducting sublayer. This diffusion barrier sublayer is intended to prevent the diffusion of components of the upper electrode into the organic electroluminescent layer, so as to prevent it from degrading. Advantageously, this diffusion barrier sublayer also serves as an upper reflection layer. Preferably, silver is used for this sublayer.

Preferably, the reflective lower layer and the semireflective upper layer define an optical cavity for the light emitted by the organic electroluminescent layer, and the distance d₆ between these layers defining this cavity is adapted so as to obtain within this, cavity, constructive interference of the light emitted.

This constructive interference advantageously promotes extraction of the emitted light through the upper electrode, thereby improving the luminous efficiency of the diode.

Preferably, said distance d₆ then approximately satisfies the following equation:

$d_{6} = {\frac{\lambda}{2n_{6}}\left( {q - \frac{\varphi_{tot}}{2\pi}} \right)}$

-   -   where q is any integer;     -   where λ is a wavelength close to maximum emittance of the         emitted light and n₆ is the average index of the organic         electroluminescent layer at this wavelength λ; and     -   where φ_(tot) is the total phase shift of a ray of emitted         light, after reflection off the reflective lower layer and off         the semireflective upper layer.

According to an embodiment relating to the semireflective upper layer, the index n₂ measured at the wavelength λ and the thickness d₂ of said dielectric antireflection layer, the index n₄ measured at the wavelength λ and the thickness d₄ of said transparent conducting first sublayer and, where appropriate, the index n₅ measured at the wavelength λ and the thickness d₅ of said semireflective upper layer are chosen in combination so that the reflectance of the stack of said layers and sublayer, measured at this wavelength λ at normal incidence, is maximum.

The dielectric antireflection layer and the transparent conducting sublayer then cooperate with the reflecting function of the semireflective upper layer to the point that it is sometimes unnecessary to have a specific semireflective upper layer.

According to another embodiment relating to the semireflective upper layer, this layer may have a multilayer dielectric structure (Bragg reflector) as described in document US 2003/184982, which is deposited on the upper electrode. This multilayer structure may serve to encapsulate the diode, as illustrated in document WO 03/052842.

Thus, by increasing, the optical cavity effect, the constructive interference in this cavity is further increased, thereby improving extraction of the emitted light and the luminous efficiency of the diode.

In practice, having chosen the material of the transparent conducting sublayer according to conductivity and transparency criteria and chosen the material and thickness of the semireflective upper layer according to performance criteria governing charge injection and barrier to diffusion into the organic electroluminescent layer, the thickness of the transparent conducting sublayer is determined so as to obtain the maximum reflectivity at normal incidence of the light emitted in the electroluminescent organic layer off the interface with the semireflective upper layer.

Preferably, said reflective lower layer is at the interface between said lower electrode and said organic electroluminescent layer, and said semireflective upper layer is at the interface between said upper electrode and said organic electroluminescent layer.

In this case, each electrode has a reflecting function.

The distance d₆ then corresponds to the thickness of the organic electroluminescent layer between the electrodes and the above equation giving the approximate value of d₆ expresses constructive interference of the light emitted in the optical cavity bounded here by the lower electrode and the upper electrode.

Preferably, the distance separating the organic electroluminescent layer from the reflective lower layer is adapted so as to obtain constructive interference between said emitted light and the light reflected off this reflective lower layer.

Preferably, said organic electroluminescent layer then comprises an emissive organic sublayer and at least one nonemissive lower organic sublayer that is interposed between said reflective lower layer and said emissive sublayer, and the thickness of the nonemissive lower organic sublayer(s) is (are) adapted so that the distance z separating the center of said emissive organic sublayer of said reflective lower layer approximately satisfies the equation:

$z = {\frac{\lambda}{2n_{6}}\left( {r - \frac{\varphi_{\inf}}{2\pi}} \right)}$

-   -   where r is any integer;     -   where λ is said wavelength close to maximum emittance of the         emitted light and n₆ is the average index of the organic         electroluminescent layer at this wavelength; and     -   where φ_(inf) is the phase shift of a ray of emitted light after         reflection off the reflective lower layer.

The center of the emissive organic sublayer corresponds to a level in this sublayer, approximately equidistant from the lower face and the upper face of this sublayer.

In general, the nonemissive lower organic sublayer or sublayers are designed to inject and/or transport carriers of a first type. The electroluminescent organic layer then preferably also comprises at least one nonemissive upper organic sublayer that is interposed between the upper electrode, and said emissive sublayer and is preferably designed to inject and/or transport carriers of a second type. The carrier types correspond to electrons and holes.

The subject of the invention is also an image display or illumination panel comprising a plurality of diodes according to the invention, characterized in that these diodes are supported by the same substrate.

Preferably, the upper electrode is then common to the plurality of these diodes. The transparent conducting sublayer of this electrode then extends over the entire active area of the panel.

Preferably, the opaque conducting sublayer of the common upper electrode forms a current-distributing grid on this electrode.

To summarize the above main features, the subject of the invention is an organic light-emitting diode and a panel comprising an array of these diodes. This diode comprises an organic electroluminescent layer interposed between a lower electrode and a partially transparent and semireflective upper electrode, which itself comprises a transparent conducting sublayer and a current-distributing metal sublayer, for example an opaque grid. A dielectric antireflection layer is deposited on the grid to improve the emission contrast in ambient light, which, according to an advantageous embodiment, is designed to optimize the semireflective properties of the upper electrode, thereby improving, by an optical cavity effect, the extraction of emitted light.

They invention will be more clearly understood on reading the following description, given by way of nonlimiting example and with reference to the appended figures in which:

FIG. 1 is a schematic cross section of an entire diode according to a first, embodiment of the invention;

FIG. 2 is a detailed cross section of the stack of organic sublayers of the diode according to FIG. 1, between the lower electrode and the upper electrode;

FIG. 3 illustrates the change in the minimum reflectivity of a metal as a function of the “theoretical” index of the material of a dielectric layer covering this metal in order to provide an antireflection function, in which each curve illustrates this change for a different metal, namely Ta, Cr, Ti, Ni and V;

FIG. 4 shows the variation of the reflectance of a stack consisting of a 15 nm calcium sublayer, an ITO sublayer of thickness d₄ and a 27 nm titanium oxide dielectric layer as a function of the thickness d₄ (in nm) of the ITO layer that are used as upper layers or sublayers in the diode according to the first embodiment, in which each curve illustrates this variation for a different wavelength, namely 636 nm for curve R, 516 nm for curve G and 452 nm for curve B;

FIG. 5 shows the variation of the light intensity (in arbitrary units) of the diode according to the first embodiment as a function of the thickness d₆ (in nm) of the organic layer of this diode, in which each curve illustrates this variation for a different emission color, namely red for curve R, green for curve G and blue for curve B;

FIG. 6 shows the variation of the reflectance of a stack consisting of a 15 nm calcium sublayer, a titanium oxide sublayer of thickness d₄ and a 27 nm titanium oxide dielectric layer as a function of the thickness d₄ (in nm) of the titanium, oxide sublayer, that are used as upper layers or sublayers in the diode according to a second embodiment of the invention; in which each curve illustrates this variation for a different wavelength, namely 636 nm for curve R, 516 nm for curve G and 452 nm for curve B; and

FIG. 7 shows the variation of the light intensity (in arbitrary units) of the diode according to the second embodiment as a function of the thickness d₆ (in nm) of the organic layer of this diode, in which each curve illustrates this variation, for a different emission color, namely red for curve R, green for curve G and blue for curve B.

A first embodiment of a diode or a diode array according to the invention will now be described with a few nonlimiting embodiments, together with a few steps in its fabrication, referring in particular to FIGS. 1 and 2.

Fabrication starts with a substrate 8, for example a glass plate or an active matrix that includes diode drivers. This substrate is provided with a reflective metal lower electrode 7 or an array of said electrodes, which are intended to act as cathodes, each lower electrode being connected to an output of a driver on the substrate. The lower layer of one or more lower electrodes, here is made of aluminum or chromium. Its thickness is about 0.1 μm.

Deposited on this lower layer of one or more reflective electrodes 7, in a manner known per se, is an organic electroluminescent layer 6 formed from the following stack, as shown in FIG. 2:

-   -   a sublayer 62 of cesium-doped 4,7-diphenyl-1,10-phenanthroline         (BPhen) for injecting and transporting electrons, having a         thickness d₆₂, that will be specified later;     -   sublayer 63 of undoped 4,7-diphenyl-1,10-phenanthroline (BPhen)         with a thickness d₆₃=10 nm, for blocking holes;     -   an emissive sublayer 61 of thickness d₆₁=20 nm, designed to emit         light when a current passes through it, for example red, green,         blue or white light, the emittance from this sublayer having a         maximum for a wavelength λ;     -   a sublayer 64 of         2,2′,7,7′tetrakis(N,N-diphenylamino)-9,9′-spiro-bifluorene         (Spiro-TAD) with a thickness d₆₄=10 nm, for blocking electrons;         and     -   a sublayer 65 of         2,2′,7,7′-tetrakis-(N,N′-di-m-methylphenylamino)-9,9′-spirobifluorene         (Spiro m-TTB) doped with a p-dopant, such as F4-TCNQ         (tetrafluorotetracyanoquinodimethane) for injecting and         transporting holes, with a thickness d₆₅ that will be specified         later.

A semireflective upper layer 5, made of silver, with a thickness d₅=15 nm approximately, is then deposited. This sublayer advantageously provides a barrier against the diffusion of atoms from the upper layers, which protects the organic electroluminescent layer 6 from a risk of degrading.

To form the upper electrode layer 11, which serves here as anode, the following are deposited:

-   -   a complete sublayer 4, that is to say without any holes         intentionally made in it, which is semitransparent and         conducting, and consists of a mixed indium tin oxide (ITO) with         a thickness d₄ that will be specified later; and     -   an opaque current-distributing metal sublayer 3 formed from an         array of parallel metal bars leaving between them large         apertures or windows for passage of the light emitted by the         electroluminescent layer 6, each bar here having a thickness d₃         equal to or greater than 100 nm. The thickness d₃ is set,         depending on the metal chosen, to obtain a surface conductivity,         at least 10 times higher than that of the ITO sublayer 4 so as         to ensure that the current flowing in the electrode is         effectively distributed. The metallic material, of the bars has         an index ñ₃ measured at the wavelength, λ_(amb) corresponding         approximately to the maximum spectral sensitivity of the eye,         i.e. about 550 nm.

Next, a transparent dielectric layer 2 of index n₂ (λ_(amb)) measured at the wavelength λ_(amb) is deposited on the upper electrode layer 11. This layer is continuous, with a uniform thickness d₂, and contains no holes except as a result of defects. This layer, designed to provide an antireflection function, is therefore in contact via its internal face with the opaque bars or zones of the current-distributing metal sublayer 3 and also with the transparent conducting sublayer 4 through the windows located between the bars of the metal sublayer 3.

The nature of the materials of the transparent conducting sublayer 4 and the dielectric antireflection layer 2 are adapted so as to protect the subjacent organic layer 6 from the risk of degrading by oxygen and/or water vapor from the ambient air. This sublayer 4 and/or this layer 2 therefore have here also the function of encapsulating the diode.

The transparent dielectric layer 2 is then in contact via its external face with a medium 1 of index n₁ measured at the wavelength λ_(amb), this material here being air. According to a first alternative embodiment (not described in detail), the diode is encapsulated in a sealed package filled with a gas or a fluid, which therefore defines the medium 1. According to a second nonlimiting alternative embodiment, an additional encapsulation layer is added on top of the transparent dielectric layer 2, the medium 1 then corresponding to the material, of this encapsulation layer.

The stack comprising, on the substrate 8, the at least one electrode of the lower layer 7, the organic electroluminescent layer 6, the upper electrode layer 11 and the antireflection layer 2, therefore forms an organic light-emitting diode or array of diodes according to one embodiment of the invention, certain parameters of which will now be specified.

According to the invention, the material of index n₂ (λ_(amb)) and the thickness d₂ of the dielectric layer 2 are chosen with the material of index ñ₃ of the opaque metal sublayer 3 so that the reflectance of the bars of the opaque metal sublayer 3, measured at λ_(amb) (about 550 nm) at normal incidence, is less than 0.1. The dielectric layer 2 then has an antireflection function with respect to the bars that form here opaque zones in the transparent upper electrode. A substantial portion of the ambient light is no longer reflected off the opaque zones of the upper electrode of the diode, thereby significantly improving the emission contrast performance of the diode in ambient light.

A first way of making this choice will now be described, but not limitingly.

FIG. 3 illustrates, for a set of metals, namely Ta, Cr, Ti, Ni and V, capable of forming the grids of the current-distributing sublayer 3, the variation in minimum reflectivity at λ_(amb) of a metal as a function of the index n₂ (λ_(amb)) of the material of a dielectric layer covering this metal in order to provide an antireflection function. The index values n₂ (λ_(amb)) of the dielectrics SiO₂, SiN and TiO₂ have been indicated.

The choice according to the invention consists in selecting a metal/dielectric pair for which the minimum reflectivity is obtained for a value n₂ ⁰ close to the value n₂ of the index of one of the dielectrics. Thus

-   -   with titanium oxide, chromium, titanium, nickel or vanadium will         be used. Among these metals, chromium will be preferred as it is         widely used in microelectronics;     -   with silicon nitride, tantalum will be used.

According to this method, the use of silica for the dielectric antireflection layer is to be avoided, at least with the metals, listed above.

A second way of making this choice will now be described, but not limitingly.

Among the general knowledge of a person skilled in the art is the fact that the index n₂ ⁰ (λ_(amb)) that the dielectric of the antireflection layer must have satisfies the following equation:

${n_{2}^{o}\left( \lambda_{amb} \right)} = \frac{\sqrt{{- \left( {{n_{1}{\cos (\varphi)}} - n_{3} + {n_{3}{\sin^{2}(\varphi)}}} \right)}n_{3}{n_{1}\left( {{n_{1}{\sin^{2}(\varphi)}} + {n_{3}{\cos (\varphi)}} - n_{1}} \right)}}}{- \left( {{n_{1}{\sin^{2}(\varphi)}} + {n_{3}{\cos (\varphi)}} - n_{1}} \right)}$

Table 1 below gives the complex index ñ₃ at λ_(amb) of various metals, namely Cr, Ta, Ti, Ni, V and Co, and the index n₂ ⁰ at λ_(amb), these being calculated according to this equation (with n₁=1). In the right-hand part of the table are the actual index values of certain dielectrics, namely SiO₂, SiN and TiO₂.

TABLE 1 Metal ñ₃ n₂ ⁰ d₂ Dielectric n₂ Cr  2.8 + 3.3 i 2.97 27 nm SiO₂ 1.5 Ta 2.74 + 1.97 i 2.23 39 nm SiN 2.0 Ti 1.79 + 2.42 i 3.03 20 nm TiO₂ 3.0 Ni 1.69 + 2.99 i 3.83 15 nm V 3.59 + 3.21 i 2.75 33 nm Co 2.02 + 3.72 i 3.95 17 nm

The choice according to the invention consists in selecting a metal/dielectric pair for which the corresponding values of n₂ ⁰ and n₂ are also as close as possible to each other. Thus:

-   -   with titanium oxide, chromium, titanium, cobalt and vanadium         will be used. Among these metals, chromium will be preferred as         it is widely used in microelectronics;     -   with silicon nitride, tantalum will be used.

According to this method, the use of silica for the dielectric antireflection layer is to be avoided, at least with the metals listed above.

For the rest of the description, the Cr—TiO₂ pair will be used.

Having chosen both the material (chromium) for the grid forming the opaque conducting sublayer 3 penetrated by windows and the material (titanium oxide) for the dielectric antireflection layer 2, it remains in particular to determine the ideal thickness d₂ of this dielectric layer.

Preferably, if φ₂₋₃ is the phase shift of a light ray of wavelength λ_(amb) after reflection at the interface between the dielectric layer 2 and the bars of the metal sublayer 3, the thickness d₂ is chosen so as to approximately satisfy the equation:

$d_{2} = {\frac{\lambda_{amb}}{4n_{2}}\left( {p - \frac{\varphi_{2 - 3}}{\pi}} \right)}$

where p is any even integer and where λ_(amb) is a wavelength close to the maximum emittance of the ambient light, generally around 550 nm. The equation thus giving the value d₂ expresses destructive interference of the ambient light within the dielectric antireflection layer above the opaque zones of the current-distributing metal layer 3.

As indicated in Table 1, a result is therefore d₂=27 nm (for p=0). The table also indicates the values d₂ (always for p=0) that would be obtained, using titanium oxide on other metals. The variations in d₂ reflect, the φ₂₋₃ values specific to each metal.

In the diode according to the invention, between the opaque zones of the upper electrode (that is to say between the bars of the grid), the organic layer 6 is coated with a stack consisting of three layers: The silver sublayer 5 of thickness d₅=15 nm, the ITO sublayer 4 of thickness d₄ and, in the opaque zones, the bars of thickness d₃> 100 nm of the current-distributing metal layer 3 or, on the windows in this layer, the titanium dioxide dielectric layer 2 of thickness d₂=27 nm. According to an advantageous variant of the invention, the thickness d₄ of the transparent conducting sublayer 4 of the upper electrode is chosen so as to obtain approximately the maximum reflectance of this stack of the light emitted by the electroluminescent layer. This reflectance is measured here at the predefined wavelength λ for which the emittance of the emissive sublayer 61 has a maximum.

The upper electrode therefore forms, in combination with the dielectric layer 2, a semireflective surface, which reflects the emitted light back towards the interior of the diode. What is therefore obtained between the two, reflective lower and semireflective upper, electrodes is an optical cavity for the light emitted at the wavelength λ in the electroluminescent layer.

Thanks to the maximum reflectance of the upper electrode with the dielectric layer 2, this optical cavity effect is enhanced, thereby improving the extraction of the light emitted and the luminous efficiency of the diode.

A method of choosing the thickness d₄ of the ITO conducting sublayer 4 will now be described in a nonlimiting manner. FIG. 4 shows the variation of the reflectance of the stack described above as a function of this thickness d₄. This figure comprises three curves, a first R for a wavelength in the red, which can be used for diodes emitting in the red, a second G for a wavelength in the green, which can be used for diodes emitting in the green, and the last B for a wavelength in the blue, which can be used for diodes emitting in the blue. A d₄ value corresponding to the maximum reflectance is chosen from this figure. Table 2 below indicates the d₄ values thus chosen: 60 nm for red, 40 nm for green and 30 nm for blue.

The equations defining the total thickness d₆ of the organic electroluminescent layer and the distance z approximately separating the center of the emissive organic sublayer 61 from the reflective lower electrode 7, which make it possible for the optical cavity effect obtained between the two electrodes to appreciably improve the extraction efficiency of the light emitted by the diode, will now be established.

Firstly, d₅ is chosen approximately such that:

$d_{6} = {\frac{\lambda}{2n_{6}}\left( {q - \frac{\varphi_{tot}}{2\pi}} \right)}$

-   -   where q is any integer;

where λ is again approximately the maximum emission wavelength of the diode;

-   -   n₆ is the average index of the organic electroluminescent layer         6 at this wavelength; and     -   where φ_(tot) is the total phase shift of an emitted light ray,         after reflection off the reflective lower electrode 7 and off         the stack, described above consisting of the three upper layers         or sublayers 5, 4, 2.

The equation fixing the approximate value of d₆ expresses constructive interference of the light, emitted in the optical cavity between the lower electrode 7 and the semireflective upper stack 5, 4, 2.

Secondly, the thickness of the sublayer 62 for injecting and/or transporting holes is chosen approximately so that the distance z is approximately equal to:

$z = {\frac{\lambda}{2n_{6}}\left( {r - \frac{\varphi_{\inf}}{2\pi}} \right)}$

-   -   where r is any integer;     -   where n₆ is the average index of the organic electroluminescent         sublayers at the wavelength λ: here, n₆=1.7; and     -   where φ_(inf) is the phase shift of a light ray emitted, after         reflection off the reflective lower electrode: here, φ_(int)=2.6         rd.

The equation fixing the approximate value of z expresses constructive interference between the light emitted in the emissive sublayer 61 and the light reflected off the reflective lower electrode 7.

The two types of interference above advantageously cooperate so as to obtain a very high light extraction factor, thereby improving the luminous efficiency of the diode.

An equivalent means for establishing the value of d₆ that provides constructive interference in the optical cavity consists in extracting this datum from one of the curves of FIG. 5, which, with the aid of a simple numerical model within the competence of a person skilled in the art or of diodes having various geometrical characteristics, gives the variations of the light intensity actually output by the diode (extracted light, in arbitrary units) as a function of the value of d₆ (in nm). The value of d₆ is chosen that gives approximately the maximum light intensity. These d₆ values are given in Table 2 below for the red, green and blue emission colors.

Since:

-   -   z= d₆₁/2+d₆₂+d₆₃, approximately: as d₆₁ (=20 nm) and d₆₃ (=10         nm) are already known, d₆₂ can therefore be deduced therefrom;         and     -   d₆=d₆₁+d₆₂+d₆₃+d₆₄+d₆₅=z+d₆₁/2+d₆₄+d₆₅: as d₆₁ (=20 nm) and d₆₄         (=10 nm) are already known, d₆₅ can therefore be deduced         therefrom.

All the values obtained are given in Table 2 for each color—red, green and blue.

The abbreviation “Int” in the last column denotes the extracted light intensity in arbitrary units.

A top-emitting light-emitting diode or array of light-emitting diodes exhibiting excellent luminous efficiency, thanks to the combination of the features specific to the invention that have just been described, is obtained.

TABLE 2 Ref. 4 λ ITO z EIL/ETL HBL EML EBL HIL/HTL Tot. Int. Color (nm) d₄ (nm) (nm) d₆₂ (nm) d₆₃ (nm) d₆₁ (nm) d₆₄ (nm) d₆₅ (nm) d₆ (nm) (a.u.) Blue 452 30 53 23 10 20 10 37 100 6.7 Green 516 40 61 31 10 20 10 44 115 6.7 Red 636 60 75 45 10 20 10 55 140 6.0

A second embodiment of the invention, which is a variant of the first embodiment described above, in which, the sole difference is that the transparent conducting sublayer 4 is made of titanium oxide instead of ITO, will now be described.

From FIG. 6, replacing FIG. 4, and from FIG. 7, replacing FIG. 5, the new results given in Table 3 are obtained in a manner similar to that described above:

TABLE 3 Ref. 4 EIL/ETL HBL EML EBL HIL/HTL λ ITO z Ref. 62 Ref. 63 Ref. 61 Ref. 64 Ref. 65 Tot. Int. Color (nm) d₄ (nm) (nm) (nm) (nm) (nm) (nm) (nm) d₆ (nm) (a.u.) Blue 452 20 53 23 10 20 10 42 105 7.1 Green 516 36 61 31 10 20 10 49 120 7.0 Red 636 38 75 45 10 20 10 65 150 6.8

The present invention also applies to an organic light-emitting diode or panel in which the charges are injected via doped organic layers. It is obvious to a person skilled in the art that the invention can be applied to other types of diodes and illumination or display panels without departing from the scope of the following claims. 

1. An organic light-emitting diode capable of emitting light, comprising: a substrate (8); an organic electroluminescent layer (6) capable of emitting light, interposed between a lower electrode and a partially transparent upper electrode, which are designed to pass a current through the organic electroluminescent layer (6) and thus cause, within this layer, the emission of light, said upper electrode comprising a transparent of semitransparent conducting sublayer (4, 5) of approximately uniform thickness and a metal sublayer (3) for distributing the current, which is distributed in opaque zones between which there are gaps in this sublayer that form windows for passage of the light emitted by the electroluminescent layer (6); and, a transparent dielectric antireflection layer (2) of approximately uniform thickness in contact, via its external face, with a medium (1), generally air, and, via its internal face, with said transparent conducting sublayer (4) and said opaque metal sublayer (3), characterized in that: the material and the thickness of said dielectric antireflection layer (2) are chosen with the material of said current-distributing metal sublayer (3) so that the reflectance of said opaque, zones, measured at normal incidence at a wavelength λ_(amb) close to 550 nm, is less than 0.1.
 2. The diode as claimed in claim 1, characterized in that, if n₁ is the optical index of said medium (1) at the wavelength λ_(amb), the material of index n₂ (λ_(amb)) measured at the wavelength λ_(amb), and the thickness d₂ of said dielectric antireflection layer (2) are chosen with the material of index n₃ of said current-distributing metal sublayer (3), which is measured at the same wavelength λ_(amb) and is defined by its argument n₃ and its phase φ in such a way that ñ₃=n₃e^(iφ), so as to approximately satisfy the equation: ${n_{2}\left( \lambda_{amb} \right)} = \frac{\sqrt{{- \left( {{n_{1}{\cos (\varphi)}} - n_{3} + {n_{3}{\sin^{2}(\varphi)}}} \right)}n_{3}{n_{1}\left( {{n_{1}{\sin^{2}(\varphi)}} + {n_{3}{\cos (\varphi)}} - n_{1}} \right)}}}{- \left( {{n_{1}{\sin^{2}(\varphi)}} + {n_{3}{\cos (\varphi)}} - n_{1}} \right)}$
 3. The diode as claimed in either of the preceding claims, characterized in that the material of index n₂ (λ_(amb)) measured at a wavelength λ_(amb) close to 550 nm, and the thickness d₂ of said dielectric antireflection layer (2) are chosen so as to approximately satisfy the $d_{2} = {\frac{\lambda_{amb}}{4{n_{2}\left( \lambda_{amb} \right)}}\left( {p - \frac{\varphi_{2 - 3}}{\pi}} \right)}$ where p is any even integer and where φ₂₋₃ is the phase shift of a light ray of wavelength λ_(amb) after reflection at the interface between the dielectric antireflection layer (2) and the current-distributing, met a sublayer (3).
 4. The diode as claimed in any one of the preceding claims, characterized in that the material of said dielectric antireflection layer (2) and the material of said current-distributing metal sublayer (3) are, respectively: either silicon nitride and tantalum; or titanium oxide and a metal from among nickel, chromium, titanium and vanadium; or zinc selenide and a metal from among nickel, chromium, titanium and vanadium.
 5. The diode as claimed in any one of claims 1 to 4, characterized in that it includes a reflective lower layer for reflecting said emitted light, which layer is interposed between said substrate and said organic electroluminescent layer (6) or is incorporated into the substrate.
 6. The diode as claimed in claim 5, characterized in that it includes an semireflective upper layer suitable for partially reflecting said emitted light, which layer is interposed between said organic electroluminescent layer (6) and the upper electrode and/or is incorporated into this upper electrode.
 7. The diode as claimed in claim 6, characterized in that, as the reflective lower layer and the semireflective upper layer define an optical cavity for the light emitted by the organic electroluminescent layer, the distance d₆ between these layers delimiting this cavity is adapted so as to obtain constructive interference of the light emitted within this cavity.
 8. The diode as claimed in claim 7, characterized in that said distance d₆ approximately satisfies the following equation: $d_{6} = {\frac{\lambda}{2n_{6}}\left( {q - \frac{\varphi_{tot}}{2\pi}} \right)}$ where q is any integer; where λ is a wavelength close to maximum emittance of the emitted light and n₆ is the average index of the organic electroluminescent layer at this wavelength λ; and where φ_(tot) is the total phase shift of a ray of emitted light, after reflection off the reflective lower layer and off the semireflective upper layer.
 9. The diode as claimed in claim 7 or 8, characterized in that the index n₂ measured at the wavelength λ and the thickness d₂ of said dielectric antireflection layer (2), the index n₄ measured at the wavelength λ and a thickness d₄ of said transparent conducting sublayer (4) and, where appropriate, the index n₅ measured at the wavelength λ and the thickness d₅ of said semireflective upper layer (5) are chosen in combination so that the reflectance of the stack of said layers and sublayers (5, 4, 2), measured at this wavelength λ at normal incidence, is maximum.
 10. The diode, as claimed in any one of claims 1 to 9, characterized in that said reflective lower layer is at the interface between said lower electrode and said organic, electroluminescent layer and in that said semireflective upper layer is at the interface between said upper electrode and said organic electroluminescent, layer.
 11. The diode as claimed in any one of claims 7 to 10, characterized in that the distance separating the organic electroluminescent layer from the reflective lower layer is adapted so as to obtain constructive interference between said emitted light and the light reflected off this reflective lower layer.
 12. The diode as claimed in claim 11, characterized in that said organic electroluminescent layer (6) comprises an emissive organic sublayer and at least one nonemissive lower organic sublayer that is interposed between said reflective lower layer and said emissive sublayer, and in that the thickness of the nonemissive lower organic sublayer(s) is (are) adapted so that the distance z separating the center of said emissive organic sublayer of said reflective lower layer approximately satisfies the equation: $z = {\frac{\lambda}{2n_{6}}\left( {r - \frac{\varphi_{\inf}}{2\pi}} \right)}$ where r is any integer; where λ is said wavelength close to maximum emittance of the emitted light and n₆ is the average index of the organic electroluminescent layer at this wavelength; and where φ_(int) is the phase shift of a ray of emitted light after reflection off the reflective lower layer.
 13. An image display or illumination panel comprising a plurality of diodes as claimed in any one of the preceding claims, characterized in that these diodes are supported by the same substrate.
 14. The panel as claimed in claim 13, characterized in that said upper electrode is common to the plurality of said diodes.
 15. The panel as claimed in claim 14, characterized in that said opaque conducting sublayer of the common upper electrode forms a current-distributing grid on this, electrode. 